Developing composition for use with photographic materials for the graphic arts

ABSTRACT

A developing agent for use in photographic materials for the graphic arts, containing an infectious developing agent and acetonitrile, malonitrile or derivatives thereof is disclosed. These nitrile compounds have improved storage stability and prevent air-oxidation.

United States atem 1 Okutsu et al.

[451 Nov. 13, 1973 DEVELOPING COMPOSITION FOR USE WITH PHOTOGRAPHICMATERIALS FOR THE GRAPHIC ARTS Inventors: Eiichi Okutsu; Yoo Iijima;Haruhiko Iwano, all of Kanagawa, Japan Fuji Photo Film Co. Ltd.,Kanagawa, Japan Filed: Mar. 31, 1972 Appl. No.: 239,978

Assignee:

Foreign Application Priority Data Mar. 31, 1971 Japan 46/19515 US. Cl96/66 R, 96/66.3, 96/665 Int. Cl G03c 5/30 Field of Search 96/66, 66.3,66.5,

Primary Examiner-Norman G. Torchin Assistant Examiner-M. F. KelleyAttorney-Richard C. Sughrue et al.

[5 7] ABSTRACT A developing agent for use in photographic materials forthe graphic arts, containing an infectious developing agent andacetonitrile, malonitrile or derivatives thereof is disclosed. Thesenitrile compounds have improved storage stability and preventair-oxidation.

14 Claims, No Drawings DEVELOPING COMPOSITION FOR USE WITHPI-IOTOGRAPHIC MATERIALS FOR THE GRAPHIC ARTS BACKGROUND OF THEINVENTION 1. Field of the Invention This invention relates to aphotographic developer for developing a photographic material for thegraphic arts. Particularly, it relates to a developer compositionprepared by incorporating acetonitrile, malonitrile or their derivativesinto an infectious developing agent, for use with a high contrastphotographic negative for the graphic arts. Air-oxidation of aninfectious developing agent is prevented and an improvement in stabilityof the developer is obtained.

2. Description of the Prior Art Photographic line and halftonereproductions are carried out by imagewise exposing a high-contrast orlitho-type silver halide photographic element through a cross-screen orcontract screen and then developing it with a developer, wherebycontinuous tone images are converted into photographic line and halftone(dot) images.

It is most desirable that the line and dot images be composed of only amaximum density portion and a background having a minimum density.However, since a high-contrast photographic element has the property offorming an intermediate density portion besides a maximum densityportion and background, a portion of intermediate density which istermed fringe is always formed around the dot images. The formation offringe is not desirable for graphic arts because it deteriorates the dotqualities.

As well known in the art, the fringe can be removed by using a so-calledinfectious developer which essentially contains a dihydroxybenzene typedeveloping agent and a small amount of sulfite ion. In a conventionaldeveloper, a dihydroxybenzene type developing agent, for example,hydroquinone is converted into quinone during development and theresulting quinone reacts with sodium bisulfite to yield sodiumhydroquinone monosulfonate. However, sodium hydroquinone monosulfonateis less reductive than hydroquinone due to its low electrode potentialand is essentially incapable of acting as a developing agent.Accordingly, development does not proceed rapidly, resulting in theformation of a fringe.

In contrast to this, in case of an infectious developing agent, theconcentration of free sulfite ions is kept low, since sodium sulfite isadded in a small amount andit reacts with a compound having carbonylgroups, such as paraformaldehyde, incorporated in the infectiousdeveloping agent, in accordance with the following equation:

CH O Na SO H O CH ONaI-ISO NaOI-I For this reason, it becomes difficultfor quinone derived from hydroquinone in a development process to reactwith sulfurous acid to produce hydroquinonemonosulfonic acid, therebythe concentration of quinone is increased. The thus produced quinone andthe original hydroquinone give rise to a disporportionation reaction andproduce semiquinone. Semiquinone reduces silver halide and itself isconverted to quinone due to its high developing activity. Yule describesin J. Frank. lnst., 239, page 221(1945) that rapid developing is broughtabout by a repetition of this procedure,

poor stability as compared to common black and white photographicdevelopers, and the life of the infectious developer is short.Consequently, when infectious developers are continuously used, imageshaving a low contrast and a high fringe are obtained because thedevelopment is not carried out rapidly. Accordingly, it has beenproposed to add an antioxidant other than sulfite to improve the storagestability. In this attempt, it is already known to add ascorbic acidinto an infectious developing solution (see Great Britian Patent No.928,390).

Ascorbic acid is, however, poor in stability and hence tends to bedecomposed. Particularly, ascorbic acid is readily decomposed when metalions such as iron ions or copper ions are present, and this leads to thepoor stability of the developing solution. Further, ascorbic acid hasthe disadvantages that the progress of the development is slowed to acertain extent and that the dot quality is reduced when it is added inan large amount.

An object of this invention is to provide a photographic developer for ahigh-contrast photographic element useful for the graphic arts having anexcellent preservative property unaccompanied by adverse influences ondot qualities.

Another object of the invention is to provide an infectious developerwhich is easily controlled before and during development.

Still another object of the invention is to provide an infectiousdeveloper in which the amount of replenishment during development isreduced.

A further object of the invention is to provide a photographicdevelopment process for the graphic arts capable of forming line and dotimages having good qualities by using an infectious developer stable fora long period of time.

SUMMARY OF THE INVENTION In order to accomplish these objects variousinvestigations have been made and it has been found that addition of atleast one kind of nitrile compound of the formula:

R1 RZ C (CHI)BCN .ai in which R R R and n are defined hereinafterincreases remarkably the storage stability of a developing solutionwithout exerting any adverse influence on the dot quality.

DETAILED DESCRIPTION OF THE INVENTION In the above formula, R R and Rwhich can be same or different, represents a hydrogen atom, alkyl groupwith not more than four carbon atoms, a halogen-substituted alkyl groupwith not more than four carbon atoms, an alkoxy group with not more thanfour carbon atoms, COOM in which M represents a hydrogen atom or awater-soluble cation, COR in which R represents an alkyl group with notmore than four carbon atoms, CONR'R" in which R and R" represent ahydrogen atom or an alkyl group with not more than four carbon atoms orCN, and n represents or an integer of from 1 to 3.

Representative compounds which can be used in the present invention areshown in the following Table, but the invention is not limited to those.

TABLE Compound l lov R R R; n l H H H 0 2 CN H H 0 3 COOH H H 0 4 OCH, HH 0 5 H H H l 6 CN H H 1 7 COONa H H l 8 OCH H H l 9 H H H 2 10 CN H H 2ll COOH H H 2 12 H H H 3 13 CN H H 3 l4- COONa H H 3 15 CH; H H 3 16 CNCH H 0 17 CN CH H 1 l8 COCH H H 0 l9 CONH H H 0 20 CH Cl H H 0 2lCONHCH, H H 0 These compounds are all known compounds and arecommerically available. However, application of the compounds of thepresent invention to photographic developing solutions has not beenknown yet, and particularly it has not been known yet to improve thestability ofa developing solution for use in a photographic material forthe graphic arts by addition of the compounds of the present inventionto such a developing solution.

As a result of investigations on various compounds, it has beendiscovered that the compounds of the above formula improve the stabilityof a developing solution for use in a photographic material for thegraphic arts. The reason why addition of these compounds improve thestability when added to a developer for the graphic arts is not yetunderstood. But, these compounds give an excellent stability and dotquality, compared to heretofore known compounds such as ascorbic acid orexcess amounts of sodium sulfite. Particularly, a slowing of developingspeed or the formation of a fringe which often accompanys the use of thehitherto known compounds is not at all observed with the compounds ofthe present invention.

The developing agent for use in a photographic material for the graphicarts can be a general infectious developing agent.

An infectious developer, in use, is basically composed of adihydroxybenzene (developing agent), an alkali, a small amount ofsulfite and, if necessary, a sulfite ion buffer. The infectiousdeveloper of the invention further contains the aforesaid compound.

Dihydroxybenzenes are known in the art and can be easily selected by oneskilled in the art. Typical examples of these compounds arehydroquinone, chlorohydroquinone, bromohydroquinone,isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2, S-dimethylhydroquinone, etc. In developingagents, hydroquinone can be practically used. These developing agentsare used singly or in combination. A suitable amount of the developingagent to be added ranges from about 5 to 50g,

preferably about 10 to 30g, per one liter of the developer.

A sulfite ion buffer can be used in such an amount that theconcentration of sulfite is maintained at a low level in the developer.Examples of such buffers are an aldehyde-alkali metal hydrogen sulfiteaddition product such as formalin-sodium hydrogen sulfite, aketonealkali metal hydrogen sulfite addition product such asacetone-sodium hydrogen sulfite addition product, and acarbonylbisulfite-amine condensation product such as sodiumbis(Z-hydroxyethyl)aminomethane sulfonate. The sulfite ion buffer is notlimited to the above examples and each ingredient of the additionproduct or condensation product may be added to the developer. Theamount of the sulfite ion buffer which is added can range from about 13to g., preferably 30 to 60g. per one liter of the developer.

An alkali is added to adjust the developer to an alkaline condition,preferably to a pH higher than 8, more preferably to a pH of 9 to l 1.Accordingly, the addition amount and kind of additive can be freelyselected and is not limited to the above examples.

The infectious developing agent in addition may contain, a pH bufferingagent such as alkanolamines, water soluble acids (e.g., acetic acid orboric acid), a water-soluble alkalis (e.g., sodium carbonate, potassiumcarbonate, sodium bicarbonate, potassium hydroxide) and salts. Yetfurther, in some cases the infectious developing agent may containorganic antifogging agents (e.g., benzotriazole, l'phenyl-S-mercaptotetrazole or nitroindazole), lithographic development inhibitingagents and oragnic solvents (e.g., triethyleneglycol, dimethylformamide,methylalcohol, or cellosolve) in an amount of not more than 300 ml per 1liter of the developing solution.

As described above, a characteristic of the infectious developingsolution is that the concentration of free sulfite ions is low. For thispurpose, a sulfite ion buffer solution such as formaldehyde-sodiumbisulfite adduct is generally employed. In general, the concentration offree sulfite ions is controlled by addition of an alkali metal sulfitesuch as sodium sulfite in an amount of not more than 5 g per 1 liter ofdeveloping solution as well as sulfite ion buffer solution. Addition ofsulfite in an amount of not more than 3 g per l liter of developingsolution is generally employed, and this improves slightly the stabilityof the developing solution, although the dot quality is reduced more orless. As described above, however, this degree of stability is notsatisfactory. On the other hand, the compounds of the present inventionimprove markedly the poor stability of the infectious developingsolution which does not contain alkali metal sulfites other than asulfite ion buffer solution such as formaldehyde-sodium sulfite adduct,and further improve outstandingly the stability infectious developingsolution which contains an alkali metal sulfite in an amount of not morethan 5 g per 1 liter of developing solution in addition to a sulfite ionbuffer agent.

One compound of the present invention or mixtures of two or morecompounds of the present invention can be employed, if desired. Theamount of the compounds of the present invention added to a developingsolution varies according to the composition of the developing solutionand the kind of the compounds of the present invention used, butgenerally the amount added is in the range of from 0.1 to 40 g per lliter of developing solution, more preferably from 0.15 g to g per 1liter of developing solution.

When developing agents are processed prior to use so tht they may bereadily used as a developing solulion on mixing with water or dissolvingin water, that is, when they are in the form of a liquid or a powdereddeveloping composition, it is effective to incorporate the compounds ofthe present invention into the developing preparation. When liquidpreparations are used, it is particularly effective to add the compoundsof the present invention since they improve markedly the stability ofliquid preparations. A representative liquid preparation generallycomprises two liquid compositions, that is, a composition which containsthe developing agent and a composition which contains the alkali agent.In this case, the compounds of the present invention may be incorporatedinto any of these compositions, but is particularly effective to addthem to the composition which contains the developing agent. Using theapproach, a liquid developing agent having excellent stability, and aninfectious developing solution prepared on dilution, having a quiteexcellent stability, can be obtained. Alternatively, in the course ofdevelopment of the photographic materials for printing or afterdevelopment, the compounds of the present invention may be added toimprove the stability of the developing solution.

The developing agents of the present invention are also suitable forhigh temperature development (i.e., a developing temperature 27C orhigher) using an automatic developing apparatus.

Light-sensitive materials for the graphic arts, which can be used in thepresent invention, include conventional silver halide emulsions (e.g.,silver chloride emulsions, silver chlorobromide emulsions, and silverchloroiodobromide emulsions). Particularly, silver chlorobromideemulsions or silver chloroiodobromide emulsions, containing not lessthan about 50 mole of silver chloride, more preferably from about 70 toabout 95 mole of silver chloride, are suitable for the presentinvention. As silver halide dispersing agents employed in theselight-sensitive materials, there may be used hydrophilic colloidalsubstances such as gelatin or gelatin derivatives (e.g., gelatin,phthalyl gelatin, malonyl gelatin); cellulose derivatives such ashydroxyethylcellulose or carboxymethylcellulose; water-soluble starchssuch as dextrin or alkali starch; hydrophilic polymers such as polyvinylalcohol, polyvinyl pyrrolidone, polyacrylamide or polystylenesulfonicacid. These light-sensitive materials further may contain hydrophobicpolymers such as polyacrylates, and gelatin plasticizers such asglycerin and trimethanol-propane.

The emulsions employed in these light-sensitive materials can besensitized on manufacture or by application in accordance with variousmethods. For example, they may be chemically sensitized according tomethods well known in the art, for example, with sodium thiosulfate,alkylthiourea, gold compounds such as complex of monovalent gold andthiocyanic acid, or

6 mixtures thereof. The emulslons further may contain heavy metals suchas platinum, palladium, iridium, rhodium or cadmium. In addition, theemulsions may be panchromatically or orthochromatically sensitized withcolor sensitizers such as cyanine dyes or merocyanine dyes. Further, theemulsions may contain dot quality improving agents such aspolyalkyleneoxides and amine compounds (as disclosed in U.S. Pat. No.3,288,612, German Specification OLS 1,932,882, U.S. Pat. No. 3,345,175)and sodium benzenethiosulfate, benzenetriazole and 1, 3, 3a,7-tetrazaindene derivatives (as disclosed in U.S. Pat. No. 3,375,114 andU.S. Pat. No. 3,333,959). The emulsions may be hardened with hardenerssuch as formaldehyde, resorcylaldehyde dimethylol urea, 2,4-dichloro-6-hydroxy-l, 3, 5- triazine (see U.S. Pat. No. 3,325,287) ormucochloric acid, and they may contain surface active agents such assaponin in order to facilitate application. The emulsions may containdevelopment progress improving agents such as 3-pyrazolidone derivativesor pyrazolone derivatives. Further, the emulsions may containdevelopment accelerating agents such as quaternary ammonium salts orcation surface-active agents. The supports which are coated with thecompounds of the present invention can be varied widely, and glass,cellulose acetate, polystyrene, polycarbonate, polyethyleneterephthalateand the like can be used.

All parts and percents set forth herein are by weight unless otherwiseindicated.

EXAMPLE 1 After photographing an exposure wedge for sensitometry,through a 150-line magenta contact screen, using a commericallithographic film comprising a film support having coated thereon asilver chlorobromoiodide emulsion (70 mol% AgCl, 0.2 mol% Agl)sensitized with gold and sulfur, spectrally sensitized with 3-carboxymethyl-S 2-( 3-ethylthiazolinilidene) ethylidene) rhodamine, andcontaining polyoxyethylenenonylphenyl ether having 50 ethyleneoxidegroups, muccochloric acid and polybutylmethacrylate, development wasconducted at 20C using four kinds of developing solutions having thefollowing compositions:

Developing Solution A Sodium Carbonate (monohydrate)50 gFormaldehyde-Sodium Bisulfite Adduct45 g Potassium Bromide-2 gHydroquinone18 g Sodium Sulfite-2 g Water to makel liter DevelopingSolution B Developing Solution B was prepared by adding 10 g ofCompound-1 of the present invention to Developing Solution A.

Developing Solution C Developing Solution C was prepared by addingadditionally 3 g of sodium sulfite to Developing Solution A. DevelopingSolution D Developing Solution D was prepared by adding 1.0 g ofascorbic acid to Developing Solution A.

The results obtained are shown in Table l.

The development time is expressed as the time required to reach thesensitivity obtained when development was conducted for 2 minutes usingDeveloping Solution A, this sensitivity being set at 100. The dotquality was graded as a, b, c, each representing good, fairly good" andbad, respectively. The aerated sensitivity was obtained by placing 500ml of developing solution in a cm X cm developing bath and contactingsuch with air for 5 hours to determine deterioration.

As can be seen from the results contained in Table 1, DevelopingSolution A with no additive shows a great decrease in sensitivity whenaerated. Developing Solution C containing 3.0 g of sodium sulfite addedshows a smaller decrease in sensitivity than Developing Solution A does,but it is greatly deteriorated and the dot quality of the fresh solutionis poor. The hitherto TABLE 2 Develop- Amount merit SensitivityDeveloping added time Dot solution Additive (g., l.) (min) quality FreshAerated F Compound-2.

known Developing Solution D containing 1.0 g of L- ascorbic acid showsalmost the same decrease in sensitivity as Developing Solution C whenaerated, but this is not completely satisfactory. On the other hand,Developing Solution B containing 10 g of Compound-1 of the presentinvention shows the smallest decrease in sensitivity when aerated, andno decrease in the dot quality was observed at all.

EXAMPLE 2 as described in Japanese application 23 ,465/65, mucochloricacid, polybutylmethacrylate prepared by emulsion polymerization asdescribed in Japanese application 5,331/70 and pentaerythritol. Themixture was then coated on a film base to manufacture the desiredlithographic film.

An exposure wedge for sensitometry was photographed through a ISO-linemagenta contact screen, using this lithographic film. The film was thentreated at 20C with the two kinds of developing solutions havingfollowing compositions.

Developing Solution E Solution 1 Distilled Water55 ml TriethyleneGlycolml Formaldehyde-Sodium Bisulfite Adductg Hydroquinonel6 gDistilled was added to make the total volume 125 The developing solutioncontaining Compound-2 shows a smaller decrease in sensitivity, comparedto the developing solution which did not contain Compound- 2.

EXAMPLE 3 After photographing an exposure wedge for sensitometry througha ISO-line magenta contact screen, using a commerical lithographic film,development was conducted at 20C, using developing solutions of thefollowing compositions:

Developing Solution G Sodium Carbonate (monohydrate)55 gFormaldehyde-Sodium Bisulfite Adduct-6O g Potassium Bromide-2 g BoricAcid-3 g Hydroquinone18 g Sodium Sulfite2 g Water to makel liter TheDeveloping Solutions H, I, J, K, L, M were prepared by adding theCompound-Ii, -4, -5, -6, -1 1, -l3 of the present invention,respectively, to Developing Solution G.

The results obtained are shown Table 3.

TABLE 3 Additive Developeom- Amount merit Sensitivity Developing poundadded time Dot solution number (gJL) (min) quality Fresh Aerated 2% a100 38 3 4. 0 2% a 100 75 4 3. 0 2% a 100 5 5. 0 2% a 1.00 90 6 3. 5 2%a 100 85 11 2. 0 2% a 100 13 2. O 2% a 100 As can be seen the developingsolutions containing the compounds of the present invention do not causea reduction in the dot quality, show only a small decrease insensitivity when aerated, and have an excellent stability.

EXAMPLE 4 Each of two 25 liter portions of a Developing Solution E asdescribed in Example 2 was placed in two developing apparatus forengraving. 200 sheets of a halfcut lithographic film were processed ineach, with 70 ml of a supplementary solution of the followingcomposition being added for each sheet of the half-cut lithographicfilm. Supplementary Solution Solution 1 Distilled Water45 ml TriethyleneGlycol-40 ml Formaldehyde-Sodium Bisulfite Adduct-45 g Hydroquinonel 8 gDistilled Water to make-125 ml Solution 2 Distilled Water-9O ml SodiumCarbonate (monohydrate)-3O g Sodium Hydroxide-5 g Potassium Bromide-2 gDistilled Water to make-125 ml The supplementary solution was preparedby adding Solution 1 and Solution 2, in order, to 750 ml of water. Toone of the automatic developing apparatus was added 20 g of Compound-9of the present invention, and both apparatus were allowed to stand for64 hours. Then, lithographic films were developed in each automaticdevelopment apparatus. No decrease in sensitivity was observed in theautomatic developing apparatus to which the compound of the presentinvention had been added. On the other hand, a great decrease insensitivity was observed in the automatic developing apparatus to whichno compound of the present invention had been added.

EXAMPLE 5 Development was conducted at 29.5C, using Developing SolutionsG, I, J, K, L, and M as described in Example 3, are using the automaticdeveloping apparatus. The results obtained are shown in Table 4.

TABLE 4 The aerated solution in Table 4 comprises a developing solutionwhich has been allowed to stand at room temperature for 64 hours in anautomatic developing apparatus. From the results it can be seen that nodeterioration of the dot quality occurs and a remarkably excellentstability is obtained with the developing solutions containingCompound-3, -4, -5, -6, -11 or -l3 of the present invention.

What is claimed is:

1. An infectious developing composition for a high contrast photographicmaterial having a silver chloride content of not less than 50 mol forthe graphic arts, comprising a dihydroxybenzene developing agent,sulfite ion in an amount up to 5g/liter, and at least one compoundhaving the following formula:

wherein R R and R which may be the same or different, each represents ahydrogen atom, an alkyl group with not more than four carbon atoms, ahalogensubstituted alkyl group with not more than four carbon atoms, analkoxy group with not more than four carbon atoms, a COOM group in whichM represents a hydrogen atom or a water-soluble cation, a COR group inwhich R represents an alkyl group with not more than 4 carbon atoms, aCONRR" group in which R and R each represents a hydrogen atom or analkyl group with not more than four carbon atoms or CN, and n represents0 or an integer of from 1 to 3.

2. The developing composition of claim 1, wherein said compositionadditionally contains an aldehydealkali metal bisulfite adduct, aketone-alkali metal bisulfite adduct or a combination thereof.

3. The developing composition of claim 2, wherein said compositioncontains formaldehyde-sodium bisulfite adduct.

4. The developing composition of claim 1, wherein said dihydroxydeveloping agent is hydroquinone, chlorohydroquinone, bromohydroquinone,isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, or 2, S-dimethylhydroquinone.

5. The developing composition of claim 4, wherein said dihydroxy-benzenedeveloping agent is hydroquinone.

6. The developing composition of claim 1, wherein said compound ispresent at a level of from 0.1 g to g per liter of developing solutionand wherein said dihydroxy developing agent is present at a levelranging from 5 to g per liter of developing solution.

7. The developing composition of claim 1, wherein R, is a hydrogen atom,a ,carboxyl group, or a cyano group, and wherein R and R are hydrogenatoms.

8. A method for forming photographic images for the graphic arts whichcomprises exposing imagewise a high contrast photographic element havinga silver chloride content not less than 50%, and developing said exposedelement in a developer composition comprising a dihydroxybenzenedeveloping agent, sulfite ion in an amount up to 5g/liter and at leastone compound having the formula:

wherein R R and R which may be the same or different, each represents ahydrogen atom, an alkyl group with not more than four carbon atoms, ahalogen-substituted alkyl group with not more than four carbon atoms, analkoxy group with not more than four carbon atoms, a COOM group in whichM represents a hydrogen atom or a water-soluble cation, a COR group inwhich R represents an alkyl group with not more than four carbon atoms,a CONR'R" group in which R and R each represents a hydrogen atom or analkyl group with not more than four carbon atoms or CN, and n represents0 or an integer of from 1 to 3.

9. The method of claim 8, wherein said composition additionally containsan aldehyde-alkali metal bisulfite adduct, a ketone-alkali metalbisulfite adduct or a combination thereof.

13. The method of claim 8, wherein said compound is present at a levelof from 0.1 g to 40 g per liter of developing solution and wherein saiddihydroxy developing agent is present at a level ranging from 5 to 50 gper liter of developing solution.

14. The method of claim 8, wherein R is a hydrogen atom, a carboxylgroup, or a cyano group, and wherein R and R are hydrogen atoms.

2. The developing composition of claim 1, wherein said compositionadditionally contains an aldehyde-alkali metal bisulfite adduct, aketone-alkali metal bisulfite adduct or a combination thereof.
 3. Thedeveloping composition of claim 2, wherein said composition containsformaldehyde-sodium bisulfite adduct.
 4. The developing composition ofclaim 1, wherein said dihydroxy developing agent is hydroquinone,chlorohydroquinone, bromohydroquinone, isopropylhydroquinone,toluhydroquinone, methylhydroquinone, 2, 3-dichlorohydroquinone, or 2,5-dimethylhydroquinone.
 5. The developing composition of claim 4,wherein said dihydroxy-benzene developing agent is hydroquinone.
 6. Thedeveloping composition of claim 1, wherein said compound is present at alevel of from 0.1 g to 40 g per liter of developing solution and whereinsaid dihydroxy developing agent is present at a level ranging from 5 to50 g per liter of developing solution.
 7. The developing composition ofclaim 1, wherein R1 is a hydrogen atom, a carboxyl group, or a cyanogroup, and wherein R2 and R3 are hydrogen atoms.
 8. A method for formingphotographic images for the graphic arts which comprises exposingimagewise a high contrast photographic element having a silver chloridecontent not less than 50%, and developing said exposed element in adeveloper composition comprising a dihydroxybenzene developing agent,sulfite ion in an amount up to 5g/liter and at least one compound havingthe formula:
 9. The method of claim 8, wherein said compositionadditionally contains an aldehyde-alkali metal bisulfite adduct, aketone-alkali metal bisulfite adduct or a combination thereof.
 10. Themethod of claim 9, wherein said composition contains formaldehyde-sodiumbisulfite adduct.
 11. The method of claim 8, wherein said dihydroxydeveloping agent is hydroquinone, chlorohydroquinone, bromohydroquinone,isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, or 2, 5-dimethylhydroquinone.
 12. The method ofclaim 11, wherein said dihydroxy-benzene developing agent ishydroquinone.
 13. The method of claim 8, wherein said compound ispresent at a level of from 0.1 g to 40 g per liter of developingsolution and wherein said dihydroxy developing agent is present at alevel ranging from 5 to 50 g per liter of developing solution.
 14. Themethod of claim 8, wherein R1 is a hydrogen atom, a carboxyl group, or acyano group, and wherein R2 and R3 are hydrogen atoms.